EP3841147B1 - Aromatic polyethers containing a biosourced furan diol - Google Patents
Aromatic polyethers containing a biosourced furan diol Download PDFInfo
- Publication number
- EP3841147B1 EP3841147B1 EP19780287.9A EP19780287A EP3841147B1 EP 3841147 B1 EP3841147 B1 EP 3841147B1 EP 19780287 A EP19780287 A EP 19780287A EP 3841147 B1 EP3841147 B1 EP 3841147B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- fluorine
- integer
- formula
- diol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 125000003118 aryl group Chemical group 0.000 title claims description 11
- 229920000570 polyether Polymers 0.000 title claims description 10
- CJMRDWKLOVHYSM-HTUGSXCWSA-N (5s,5as,8ar,9s)-5,7,7-trimethyl-4,5a,6,8,8a,9-hexahydroazuleno[5,6-c]furan-5,9-diol Chemical compound C[C@]1(O)CC2=COC=C2[C@@H](O)[C@@H]2CC(C)(C)C[C@@H]21 CJMRDWKLOVHYSM-HTUGSXCWSA-N 0.000 title description 2
- CJMRDWKLOVHYSM-UHFFFAOYSA-N 8-epi-furandiol Natural products CC1(O)CC2=COC=C2C(O)C2CC(C)(C)CC21 CJMRDWKLOVHYSM-UHFFFAOYSA-N 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims description 115
- 238000000034 method Methods 0.000 claims description 35
- 239000012528 membrane Substances 0.000 claims description 34
- TVYABKWHFSGGMF-UHFFFAOYSA-N [2-(hydroxymethyl)oxolan-3-yl]methanol Chemical compound OCC1CCOC1CO TVYABKWHFSGGMF-UHFFFAOYSA-N 0.000 claims description 33
- 150000001491 aromatic compounds Chemical class 0.000 claims description 31
- 239000011737 fluorine Substances 0.000 claims description 28
- 229910052731 fluorine Inorganic materials 0.000 claims description 28
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 22
- 125000001153 fluoro group Chemical group F* 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical group 0.000 claims description 15
- 239000000460 chlorine Chemical group 0.000 claims description 14
- 229910052801 chlorine Chemical group 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- -1 alkali metal salts Chemical class 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 32
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 24
- 150000003457 sulfones Chemical class 0.000 description 20
- 229920006393 polyether sulfone Polymers 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 9
- 229960002479 isosorbide Drugs 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 229940082150 encore Drugs 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- 239000004695 Polyether sulfone Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920005604 random copolymer Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000001542 size-exclusion chromatography Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006184 cosolvent Substances 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BWQOPMJTQPWHOZ-UHFFFAOYSA-N (2,3-difluorophenyl)-phenylmethanone Chemical compound FC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1F BWQOPMJTQPWHOZ-UHFFFAOYSA-N 0.000 description 2
- GKPHNZYMLJPYJJ-UHFFFAOYSA-N 2,3-difluorobenzonitrile Chemical compound FC1=CC=CC(C#N)=C1F GKPHNZYMLJPYJJ-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003880 polar aprotic solvent Substances 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- ZDULHUHNYHJYKA-UHFFFAOYSA-N 2-propan-2-ylsulfonylpropane Chemical compound CC(C)S(=O)(=O)C(C)C ZDULHUHNYHJYKA-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- ZOSVFAIIFHTUEG-UHFFFAOYSA-L dipotassium;dihydroxide Chemical compound [OH-].[OH-].[K+].[K+] ZOSVFAIIFHTUEG-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical class OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- TZSNRSDBFFRMEM-UHFFFAOYSA-N methanol;oxolane Chemical compound OC.OC.C1CCOC1 TZSNRSDBFFRMEM-UHFFFAOYSA-N 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920006301 statistical copolymer Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4056—(I) or (II) containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
Definitions
- the present invention relates to an aromatic polyether type polymer based on a biosourced furan diol, a process for preparing said polymer, as well as the use of said polymer for the manufacture of membranes for manufactured parts and coatings.
- Aromatic polyethers such as polyethersulfones, polyetherketones and polyetherbenzonitriles, are recognized as high-performance polymers due to their excellent thermal stabilities and mechanical properties.
- the main application of these polymers is liquid and gas phase separation membranes.
- the polyethersulfones available on the market are notably synthesized from aromatic diols such as bisphenol A or 4,4'-dihydroxyphenyl with dichlorodiphenyl sulfone. Industrialists have thus been interested in partially replacing aromatic diols with a diol coming from biomass such as isosorbide.
- Kricheldorf et al. first described the preparation and characterization of isosorbide-containing polyethersulfones from silylated isosorbide and difluorodiphenylsulfone ( H. Kricheldorf et al., J. Polymer Sci., Part A: Polym. Chem., 1995, 33, 2667-2671 ). Since silylated isosorbide is expensive, Kricheldorf and Chatti have modified their polymerization conditions and described the synthesis of isosorbide-containing polyethersulfones from non-functionalized isosorbide and difluorodiphenylsulfone ( S. Chatti et al., High Perform. Polym., 2009, 21, 105-118 ).
- Belgacem et al. then described the synthesis of polyethersulfones containing a 1,4:3,6-dianhydrohexitol and bisphenol A, from difluorodiphenylsulfone, a 1,4:3,6-dianhydrohexitol and bisphenol A as monomers react together in the same reaction medium ( Belgacem et al., Des. Monomers Polym., 2016, 19, 248-255 ). Under these conditions, the polymer obtained is a random copolymer in which the sequence of units containing 1,4:3,6-dianhydrohexitol and bisphenol A is random.
- Kanetaka et al. described the synthesis of polyether ketones from a 2,5-furanedicarboxylic acid derivative ( Kanetaka et al., J. Pol. Sci., 2016, 54, 3094-3101 ).
- polymers of this type having characteristics suitable for use in the manufacture of membranes. These characteristics are, for example, high number average molecular weights (Mn) which are necessary to obtain film-forming properties.
- Mn number average molecular weights
- These polymers can also advantageously have significant hydrophilicity: in the case of a membrane, it will humidify quickly, which leads to rapid filtration with high flow rates and yields.
- these polymers can also have permeability properties, and in particular selectivity with respect to certain gases and/or liquids, which can prove particularly interesting, in membrane filtration processes.
- the invention also relates to a process for preparing the aromatic polyether type polymer comprising the repeat unit(s) of formula I, comprising a reaction step between tetrahydrofuran dimethanol, optionally in the presence of a co-diol, with a compound dihalogenated aromatic in the presence of a base in an organic solvent.
- Another object of the present invention relates to the use of the polymer according to the invention for the manufacture of membranes.
- the polymer of formula I can be in the form of a random copolymer or in the form of a homopolymer.
- the polymer according to the invention is in the form of a random copolymer.
- random copolymer is meant for the purposes of the present invention a polymer resulting from the copolymerization of at least two types of monomer, chemically different, called co-monomers.
- a statistical copolymer is therefore formed of at least two repeating units linked together randomly.
- the polymer according to the invention is in the form of a homopolymer.
- the term “homopolymer” means a polymer derived from a single species of monomer. All the repeating units of a homopolymer are therefore of the same chemical nature.
- the average molecular mass of the polymer of formula (I) is between 1,000 and 150,000 g/mol.
- a particular class of polymers which are the subject of this Application are the polymers of formula (I) as defined above, the average molecular mass of which is between 40,000 and 150,000 g/mol, preferably between 70,000 and 150,000. g/mol.
- the pattern Ar is as follows:
- pattern D is as follows:
- the invention also relates to a process for preparing the aromatic polyether type polymer comprising the repeating unit(s) of formula ( I ).
- the process for preparing the polymer comprising the repeating unit(s) of formula ( I ) comprises a reaction step between tetrahydrofuran dimethanol, optionally in the presence of a co-diol HO- D -OH, with a dihalogenated aromatic compound - Ar -X in the presence of a base in an organic solvent.
- the co-diols and dihalogenated aromatic compounds which can be used are those described above.
- the process of the invention makes it possible to control the molar ratio between the tetrahydrofuran dimethanol and the dihalogenated aromatic compound so as to obtain polymers having high hydrophilicity and/or good permeability properties.
- the average molecular mass of the polymer of formula (I) is between 1,000 and 150,000 g/mol.
- a particular class of polymers which are the subject of this Application are the polymers of formula (I) mentioned above, the average molecular mass of which is between 40,000 and 150,000 g/mol, preferably between 70,000 and 150,000 g/mol.
- Variants of the process according to the invention are the variants which lead to the polymers of formulas ( II ), ( III ), ( IV ) and ( V ), by making the choices relating to the compounds X- Ar -X and HO- D -OH, at the ratio m/n and at the integer p, which have been explained previously, with regard to said polymers of formulas ( II ), ( III ), ( IV ) and ( V ). These choices therefore apply mutatis mutandis to the different variants of the process according to the invention.
- reaction between tetrahydrofuran dimethanol, and optionally a co-diol, with the dihalogenated aromatic compound is carried out in the presence of a base in an organic solvent and makes it possible to form the polymer of the invention.
- the base is advantageously chosen from alkali metal salts.
- the base is chosen from potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), cesium carbonate (CsCO 3 ), lithium carbonate (LiCO 3 ), methanolate potassium, sodium methanolate, potassium ethanolate, potassium tert- butoxide, potassium tert -pentylate, potassium bis(trimethyl)silanolate, potassium bis(trimethylsilyl)amide, potassium hydroxide potassium, sodium hydroxide, and sodium hydride.
- the base is chosen from potassium carbonate and sodium carbonate. Even more preferably, the base is potassium carbonate and sodium carbonate.
- the proportion of base is between 1 and 3 mole equivalents relative to the total quantity of tetrahydrofuran dimethanol and co-diol.
- the proportion of base is approximately 2 mole equivalents relative to the total quantity of tetrahydrofuran dimethanol and co-diol.
- the organic solvent is advantageously chosen from polar aprotic solvents.
- aprotic polar solvent is meant for the purposes of the present invention a solvent having a dipole moment without an acidic hydrogen atom, that is to say linked to a heteroatom.
- the solvent is chosen from polar aprotic solvents comprising a sulfur atom or a nitrogen atom.
- the solvent is chosen from dimethylsulfoxide, diethylsulfoxide, sulfolane, dimethylsulfone, diethylsulfone, diphenylsulfone, diisopropylsulfone, tetrahydrothiophene-1-monoxide, dimethylacetamide, dimethylformamide, N-methyl-2- pyrrolidone, and N-cyclohexyl-2-pyrrolidone, alone or in mixture. More preferably, the solvent is chosen from N-methyl-2-pyrrolidone and dimethyl sulfoxide, alone or as a mixture. Even more preferably, the solvent is dimethyl sulfoxide or N-methyl-2-pyrrolidone.
- a co-solvent may be added to the organic solvent.
- the co-solvent is advantageously chosen from toluene, benzene, chlorobenzene, tetrahydrofuran, alone or as a mixture.
- the co-solvent is toluene.
- the polymer is formed by reaction between tetrahydrofuran dimethanol, optionally a co-diol, and the dihalogenated aromatic compound as monomers.
- the total proportion of monomers that is to say the sum of the quantity of tetrahydrofuran dimethanol, co-diol and dihalogenated aromatic compound, is between 10% and 50%, preferably between 20% and 40%. % by mass relative to the sum of the mass of the solvent and the mass of the monomers. More preferably, the proportion of monomers is approximately 30% by weight relative to the sum of the mass of the solvent and the mass of the monomers.
- the reaction medium comprising tetrahydrofuran dimethanol, optionally a co-diol and the dihalogenated aromatic compound to form the polymer
- the reaction medium comprising tetrahydrofuran dimethanol, optionally a co-diol, and the compound dihalogenated aromatic is heated.
- the preparation of the polymer is carried out at a temperature between 160°C and 240°C, preferably between 190°C and 230°C, more preferably between 200°C and 220°C, for a period of between 30 minutes and 12 hours, preferably between 30 minutes and 6 hours, more preferably between 1 hour and 3 hours. Even more preferably, the polymer is produced at a temperature of approximately 210° C., for a period of approximately 2 hours.
- the polymer obtained can be precipitated by techniques known to those skilled in the art, such as for example the precipitation of the reaction medium in a large volume of water, approximately 10 times the volume of the reaction medium.
- the polymer can then be dried according to techniques known to those skilled in the art, for example in an oven at 80°C for 12 hours.
- the resulting polymer can finally, optionally, undergo post-treatment steps, in particular with a view to increasing its purity or improving certain of its properties.
- Another object of the present invention relates to the use of the polymer according to the invention for the manufacture of membranes, manufactured parts and coatings.
- Membranes can be manufactured from the polymer according to the invention according to techniques known to those skilled in the art.
- the membranes obtained with the polymer according to the invention have interesting hydrophilic and gas permeability properties.
- the membranes can be in the form of porous or non-porous films.
- the membranes can be manufactured in the form of monofilament or hollow fibers.
- the polymer according to the invention can be used in aqueous media, including body fluids.
- the polymer according to the invention is biocompatible and can therefore be used in the form of a membrane in the medical environment such as for hemodialysis or in the consumer environment (food and drinks), in the wastewater treatment environment.
- Porous membranes in the form of tubes or hollow fibers can have different pore sizes known to those skilled in the art depending on their applications (microfiltration, ultrafiltration, nanofiltration, reverse osmosis).
- the performance of the aqueous membranes obtained with the polymer according to the invention can be improved by techniques known to those skilled in the art, in particular the use of monomers sulfonated or post-treatment of membranes by sulfonation or surface treatment to prevent clogging.
- Gas phase membranes can be used for the production of nitrogen from the separation of the mixture of nitrogen and oxygen from the air, and the production of methane from the separation of methane and CO 2 .
- Membranes in the form of films or plates can be used for optics or packaging.
- Molded parts can be manufactured from the polymer of the invention according to techniques known to those skilled in the art. Injection molding of the polymer according to the invention can lead to the production of parts used in the health sector, with dental applications to replace metals, glass and other disposable or reusable utensils, but also in the sector aeronautics, electronics and automobiles.
- Another object of this invention is the use of the polymer of the invention as a metal coating resin to prevent corrosion.
- the coating obtained from the polymer according to the invention can be applied to steel, aluminum, copper, metals used in the consumer sector (food and beverage), the marine sector with the hulls of boats , the aerospace, automotive, electrical with cables and electronics with circuits sectors.
- the resin obtained from the polymer according to the invention can also be applied to other substrates such as glass or carbon fiber to form a composite after evaporation of the resin solvent.
- the composites formed from the polymer resin according to the invention can be used in the aerospace and automotive fields to replace metal parts.
- Example 1 General procedure for preparing a copolymer according to the invention
- the tetrahydrofuran dimethanol and optionally a co-diol (5 mmol in total), the dihalogenated aromatic compound (5 mmol) and the potassium carbonate (1.3961 g, 10 mmol) are introduced into a 100 mL three-necked flask equipped with a stirring blade, a nitrogen inlet and outlet to avoid oxidation.
- the whole is dissolved in DMSO (5 mL) and is brought to 210°C with stirring at 50 rpm. After 2 h to 9 h of heating at 210°C, the medium is diluted with 10 mL of DMSO. When the medium has returned to room temperature, the polymer is precipitated in 100 mL of distilled water in a beaker with magnetic stirring. After 1 hour of stirring, the polymer is recovered by Büchner filtration and then dried in an oven for 12 hours at 80°C. The polymer is analyzed by SEC, 1 H NMR and DSC.
- the 100MHz 13 C spectra were carried out on a Brüker Ascend TM 400 in a 5mm glass tube in DMSO- d 6 .
- the differential scanning calorimetry analysis was carried out on a DSC-Q5000 SA, TA Instruments, USA with a flow rate of 50ml/min with nitrogen at 10°C/min or 20°C/min from 20°C to 300°C and in a pierced aluminum crucible.
- Polymer 1 is prepared according to the general procedure above from tetrahydrofuran dimethanol (5 mmol) and difluorodiphenyl sulfone (5 mmol) as a dihalogenated aromatic compound.
- Polymer 2 is prepared according to the general procedure above from tetrahydrofuran dimethanol (5 mmol) and dichlorodiphenyl sulfone (5 mmol) as a dihalogenated aromatic compound.
- Polymer 3 is prepared according to the general procedure above from tetrahydrofuran dimethanol (5 mmol) and difluorobenzonitrile (5 mmol) as a dihalogenated aromatic compound.
- Polymer 4 is prepared according to the general procedure above from tetrahydrofuran dimethanol (5 mmol) and difluorobenzophenone (5 mmol) as a dihalogenated aromatic compound.
- Polymer 5 is prepared according to the general procedure above from tetrahydrofuran dimethanol (1 mmol), Bisphenol A (4 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as dihalogenated aromatic compound. .
- Polymer 6 is prepared according to the general procedure above from tetrahydrofuran dimethanol (1.25 mmol), Bisphenol A (3.75 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as as a dihalogenated aromatic compound.
- Polymer 7 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2 mmol), Bisphenol A (3 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as dihalogenated aromatic compound. .
- Polymer 8 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2.5 mmol), Bisphenol A (2.5 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as as a dihalogenated aromatic compound.
- Polymer 9 is prepared according to the general procedure above from tetrahydrofuran dimethanol (3 mmol), Bisphenol A (2 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as dihalogenated aromatic compound. .
- Polymer 10 is prepared according to the general procedure above from tetrahydrofuran dimethanol (4 mmol), Bisphenol A (1 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as dihalogenated aromatic compound. .
- Polymer 11 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2.5 mmol), 4,4'-dihydroxydiphenyl (2.5 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as a dihalogenated aromatic compound.
- Polymer 12 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2.5 mmol), Bisphenol S (2.5 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as as a dihalogenated aromatic compound.
- Polymer 13 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2.5 mmol), isosorbide (2.5 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as as a dihalogenated aromatic compound.
- Polymer 14 a polyethersulfone purchased from ACROS ORGANICS 178910050 in the form of transparent granules. This product is a polyethersulfone based on bisphenol A and a diphenyl sulfone derivative.
- Example 2 General procedure for preparing membranes from polymers according to the invention and comparison with a membrane obtained from a commercial polymer
- a membrane is prepared from a solution of the polymer at 20% m in NMP cast on a glass plate. The solvent is then evaporated using the following thermal cycle: 50°C for 12 h, 80°C for 1 h, 120°C for 1 h, 150°C for 1 h and 200°C for 2 h. After cooking a membrane is obtained.
- Membranes were prepared according to the general procedure above from polymers 1, 6 and 8 according to the invention in comparison with a membrane prepared from a commercial polymer.
- the contact angle of the membranes prepared from polymers 1 and 8 according to the invention was measured with water and diiodomethane according to the model of Owens, Wendt, Rabel and Kaelble.
- the water recovery measurement was carried out with a Dynamic Vapor Sorption device (DVS Q-5000 SA, TA Instruments) at atmospheric pressure and at the isotherm of 21°C with a sorption/desorption cycle from 0 to 90 % humidity.
- a Dynamic Vapor Sorption device (DVS Q-5000 SA, TA Instruments) at atmospheric pressure and at the isotherm of 21°C with a sorption/desorption cycle from 0 to 90 % humidity.
- the hydrophilicity of the polymers according to the invention increases as a function of the rate of incorporation of tetrahydrofuran dimethanol.
- measuring the contact angle of the membranes prepared from polymers 1 and 8 makes it possible to attest to the wettability of the films containing THFDM compared to the PES reference.
- Increasing the surface energy as a function of the tetrahydrofuran dimethanol incorporation rate allows the creation of stronger interactions of the polymer film with the water drop. This thus leads to a reduction in the contact angle of the water as a function of the rate of incorporation of tetrahydrofuran dimethanol.
- the polymers according to the invention have a water adsorption capacity much greater than the reference: this much more marked hydrophilicity is particularly advantageous for a membrane, whose capacity to hydrate quickly goes condition its performance and effectiveness.
- the experiments are carried out at room temperature.
- the manipulation consists of inserting the film to be studied into the permeation cell.
- the permeation experiment consists of imposing a pressure (3 bar) of a chosen gas in the upstream compartment of the cell and measuring the rise in pressure in the downstream compartment of the cell. Permeability is calculated from the slope of the pressure versus time line in the steady state, corrected for static vacuum if necessary.
- the gas permeation properties of the membranes prepared from polymer 6 according to the invention were measured. The results are presented in Table 3.
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Description
La présente invention concerne un polymère de type polyéther aromatique à base d'un diol biosourcé furanique, un procédé de préparation dudit polymère, ainsi que l'utilisation dudit polymère pour la fabrication de membranes de pièces manufacturées et de revêtements.The present invention relates to an aromatic polyether type polymer based on a biosourced furan diol, a process for preparing said polymer, as well as the use of said polymer for the manufacture of membranes for manufactured parts and coatings.
L'industrie chimique, qui reste largement basée sur les ressources fossiles, entre dans une phase de transition vers l'utilisation de matières premières biosourcées plus durables. L'augmentation des prix des matières premières fossiles et les préoccupations environnementales croissantes, telles que les émissions de gaz à effet de serre, poussent la recherche académique et industrielle à explorer l'utilisation de la biomasse pour la production durable de carburants et de produits chimiques. Le développement de polymères biosourcés et d'autres matériaux suit la même tendance et constitue un domaine émergent et important.The chemical industry, which remains largely based on fossil resources, is entering a transition phase towards the use of more sustainable bio-sourced raw materials. Rising prices of fossil raw materials and growing environmental concerns, such as greenhouse gas emissions, are driving academic and industrial research to explore the use of biomass for sustainable production of fuels and chemicals . The development of bio-based polymers and other materials follows the same trend and is an emerging and important area.
Les polyéthers aromatiques, tels que les polyéthersulfones, les polyéthercétones et les polyétherbenzonitriles, sont reconnus comme étant des polymères de haute performance du fait de leurs excellentes stabilités thermiques et propriétés mécaniques. Ces polymères ont pour principale application les membranes de séparation en phase liquide et gazeuse. Les polyéthersulfones disponibles sur le marché sont notamment synthétisés à partir de diols aromatiques tels que le bisphénol A ou le 4,4'-dihydroxyphényle avec la dichlorodiphényle sulfone. Les industriels se sont ainsi intéressés à substituer partiellement les diols aromatiques par un diol provenant de la biomasse tels que l'isosorbideAromatic polyethers, such as polyethersulfones, polyetherketones and polyetherbenzonitriles, are recognized as high-performance polymers due to their excellent thermal stabilities and mechanical properties. The main application of these polymers is liquid and gas phase separation membranes. The polyethersulfones available on the market are notably synthesized from aromatic diols such as bisphenol A or 4,4'-dihydroxyphenyl with dichlorodiphenyl sulfone. Industrialists have thus been interested in partially replacing aromatic diols with a diol coming from biomass such as isosorbide.
Ainsi, Kricheldorf et al. ont d'abord décrit la préparation et la caractérisation de polyéthersulfones contenant de l'isosorbide à partir d'isosorbide silylé et de difluorodiphénylsulfone (
Belgacem et al. ont ensuite décrit la synthèse de polyéthersulfones contenant un 1,4:3,6-dianhydrohexitol et du bisphénol A, à partir de difluorodiphénylsulfone, d'un 1,4:3,6-dianhydrohexitol et de bisphénol A en tant que monomères mis à réagir ensemble dans le même milieu réactionnel (
La demande
Par ailleurs, Kanetaka et al. ont décrit la synthèse de polyéthercétones à partir d'un dérivé d'acide 2,5-furanedicarboxylique (
Demeure toutefois et de manière générale, la volonté de l'homme du métier d'enrichir la bibliothèque de polymères de type polyéthers aromatiques obtenus à partir d'un diol biosourcé et ce, dans une démarche d'économie des matériaux fossiles, au profit de matières premières biosourcées.However, in general, there remains the desire of those skilled in the art to enrich the library of polymers of the aromatic polyethers type obtained from a biosourced diol, in an approach to saving fossil materials, for the benefit of biosourced raw materials.
De manière particulière, il existe aussi un besoin de fournir des polymères de ce type, présentant des caractéristiques aptes à les utiliser dans la fabrication de membranes. Ces caractéristiques sont, par exemple, des masses moléculaires moyennes en nombre (Mn) élevées qui sont nécessaires à l'obtention de propriétés filmogènes. Ces polymères peuvent aussi présenter de manière avantageuse une hydrophilie importante : dans le cas d'une membrane, celle-ci va s'humidifier rapidement, ce qui conduit à une filtration rapide avec des débits et des rendements élevés. Enfin, ces polymères peuvent aussi présenter des propriétés de perméabilité, et notamment de sélectivité vis-à-vis de certains gaz et/ou liquides, qui peuvent s'avérer particulièrement intéressantes, dans des procédés de filtration membranaires.In particular, there is also a need to provide polymers of this type, having characteristics suitable for use in the manufacture of membranes. These characteristics are, for example, high number average molecular weights (Mn) which are necessary to obtain film-forming properties. These polymers can also advantageously have significant hydrophilicity: in the case of a membrane, it will humidify quickly, which leads to rapid filtration with high flow rates and yields. Finally, these polymers can also have permeability properties, and in particular selectivity with respect to certain gases and/or liquids, which can prove particularly interesting, in membrane filtration processes.
L'invention concerne un polymère de type polyéther aromatique de formule (I) comprenant un motif de répétition formé à partir d'un diol biosourcé furanique et d'un composé aromatique dihalogéné X-Ar-X, et un second motif de répétition formé à partir d'un co-diol HO-D-OH et d'un composé aromatique dihalogéné X-Ar-X :
- m est un nombre entier supérieur à 1
- n est 0 ou un nombre entier supérieur à 1
- le ratio m/n est compris entre 100/0 et 1/99
- p est un nombre entier supérieur à 1
- Ar provient du composé aromatique dihalogéné et est sélectionné dans le groupe constitué de :
- D provient du co-diol et est sélectionné dans le groupe constitué de :
- X est un halogène, de préférence X est choisi parmi le fluor et le chlore, de préférence encore X est le fluor.
- m is an integer greater than 1
- n is 0 or an integer greater than 1
- the m/n ratio is between 100/0 and 1/99
- p is an integer greater than 1
- Ar comes from the dihalogenated aromatic compound and is selected from the group consisting of:
- D comes from the co-diol and is selected from the group consisting of:
- X is a halogen, preferably X is chosen from fluorine and chlorine, more preferably X is fluorine.
L'invention concerne également un procédé de préparation du polymère de type polyéther aromatique comprenant le ou les motifs de répétition de la formule I, comprenant une étape de réaction entre le tetrahydrofurane diméthanol, optionnellement en présence d'un co-diol, avec un composé aromatique dihalogéné en présence d'une base dans un solvant organique.The invention also relates to a process for preparing the aromatic polyether type polymer comprising the repeat unit(s) of formula I, comprising a reaction step between tetrahydrofuran dimethanol, optionally in the presence of a co-diol, with a compound dihalogenated aromatic in the presence of a base in an organic solvent.
Un autre objet de la présente invention concerne l'utilisation du polymère selon l'invention pour la fabrication de membranes.Another object of the present invention relates to the use of the polymer according to the invention for the manufacture of membranes.
L'invention concerne un polymère de type polyéther aromatique de formule (I) comprenant un motif de répétition formé à partir d'un diol biosourcé furanique et d'un composé aromatique dihalogénéX-Ar-X, et optionnellement un second motif de répétition formé à partir d'un co-diol HO-D-OH et d'un composé aromatique dihalogéné X-Ar-X :
- m est un nombre entier supérieur à 1
- n est 0 ou un nombre entier supérieur à 1
- le ratio m/n est compris entre 100/0 et 1/99
- p est un nombre entier supérieur à 1
- Ar est sélectionné dans le groupe constitué de :
- D est sélectionné dans le groupe constitué de :
- X est un halogène, de préférence X est choisi parmi le fluor et le chlore, de préférence encore X est le fluor.
- m is an integer greater than 1
- n is 0 or an integer greater than 1
- the m/n ratio is between 100/0 and 1/99
- p is an integer greater than 1
- Ar is selected from the group consisting of:
- D is selected from the group consisting of:
- X is a halogen, preferably X is chosen from fluorine and chlorine, more preferably X is fluorine.
Il est du mérite des inventeurs d'avoir mis en évidence que l'incorporation de tetrahydrofurane diméthanol dans la chaîne de polymère permet d'améliorer le caractère hydrophile du polymère de l'invention. Cette hydrophilie importante est une propriété particulièrement intéressante pour la fabrication de membranes de filtration : ladite membrane va s'humidifier rapidement, ce qui conduit à une filtration rapide avec des débits et des rendements élevés. La présence de tetrahydrofurane diméthanol dans le polymère de l'invention permet également d'obtenir de bonnes propriétés de perméabilité.It is to the merit of the inventors to have demonstrated that the incorporation of tetrahydrofuran dimethanol in the polymer chain makes it possible to improve the hydrophilic character of the polymer of the invention. This significant hydrophilicity is a particularly interesting property for the manufacture of filtration membranes: said membrane will humidify quickly, which leads to rapid filtration with high flow rates and yields. The presence of tetrahydrofuran dimethanol in the polymer of the invention also makes it possible to obtain good permeability properties.
Le polymère de la formule I peut se présenter sous la forme d'un copolymère statistique ou sous la forme d'un homopolymère.The polymer of formula I can be in the form of a random copolymer or in the form of a homopolymer.
Lorsque le ratio m/n est compris entre 99/1 et 1/99, le polymère selon l'invention se présente sous la forme d'un copolymère statistique. Par « copolymère statistique » on entend au sens de la présente invention un polymère issu de la copolymérisation d'au moins deux types de monomère, chimiquement différents, appelés co-monomères. Un copolymère statistique est donc formé d'au moins deux motifs de répétition enchaînés de manière aléatoire.When the m/n ratio is between 99/1 and 1/99, the polymer according to the invention is in the form of a random copolymer. By “random copolymer” is meant for the purposes of the present invention a polymer resulting from the copolymerization of at least two types of monomer, chemically different, called co-monomers. A statistical copolymer is therefore formed of at least two repeating units linked together randomly.
Lorsque le ratio m/n est de 100/0, le polymère selon l'invention se présente sous la forme d'un homopolymère. Par « homopolymère » on entend au sens de la présente invention un polymère issu d'une seule espèce de monomère. Tous les motifs de répétition d'un homopolymère sont donc de même nature chimique.When the m/n ratio is 100/0, the polymer according to the invention is in the form of a homopolymer. For the purposes of the present invention, the term “homopolymer” means a polymer derived from a single species of monomer. All the repeating units of a homopolymer are therefore of the same chemical nature.
De manière générale, la masse moléculaire moyenne du polymère de la formule (I) est comprise entre 1 000 et 150 000 g/mol,.Generally speaking, the average molecular mass of the polymer of formula (I) is between 1,000 and 150,000 g/mol.
Une classe particulière de polymères objets de la présente Demande sont les polymères de formule (I) telle que définie ci-dessus, dont la masse moléculaire moyenne est comprise entre 40 000 et 150 000 g/mol, de préférence entre 70 000 et 150 000 g/mol.A particular class of polymers which are the subject of this Application are the polymers of formula (I) as defined above, the average molecular mass of which is between 40,000 and 150,000 g/mol, preferably between 70,000 and 150,000. g/mol.
Des polymères préférés selon l'invention sont des polymères de formule (I) suivante
- m est un nombre entier supérieur à 1
- n est 0 ou un nombre entier supérieur à 1
- le ratio m/n est compris entre 100/0 et 1/99, de préférence entre 100/0 et 10/90
- p est un nombre entier supérieur à 1
- Ar est sélectionné dans le groupe constitué de :
- D est sélectionné dans le groupe constitué de :
- X est un halogène, de préférence X est choisi parmi le fluor et le chlore, de préférence encore X est le fluor.
- m is an integer greater than 1
- n is 0 or an integer greater than 1
- the m/n ratio is between 100/0 and 1/99, preferably between 100/0 and 10/90
- p is an integer greater than 1
- Ar is selected from the group consisting of:
- D is selected from the group consisting of:
- X is a halogen, preferably X is chosen from fluorine and chlorine, more preferably X is fluorine.
Dans un mode de réalisation plus préféré, le motif Ar est le suivant :
Selon ce mode de réalisation, le polymère de l'invention est celui comprenant les motifs de répétition de la formule (II) suivante :
- m est un nombre entier supérieur à 1
- n est 0 ou un nombre entier supérieur à 1
- le ratio m/n est compris entre 100/0 et 1/99, de préférence entre 100/0 et 10/90
- p est un nombre entier supérieur à 1
- D est sélectionné dans le groupe constitué de :
- X est un halogène, de préférence X est choisi parmi le fluor et le chlore, de préférence encore X est le fluor.
- m is an integer greater than 1
- n is 0 or an integer greater than 1
- the m/n ratio is between 100/0 and 1/99, preferably between 100/0 and 10/90
- p is an integer greater than 1
- D is selected from the group consisting of:
- X is a halogen, preferably X is chosen from fluorine and chlorine, more preferably X is fluorine.
Dans un autre mode de réalisation plus préféré, le motif D est le suivant :
Selon ce mode de réalisation, le polymère selon l'invention est celui comprenant les motifs de répétition de la formule (III) suivante :
- m est un nombre entier supérieur à 1
- n est 0 ou un nombre entier supérieur à 1
- le ratio m/n est compris entre 100/0 et 1/99, de préférence entre 100/0 et 10/90
- p est un nombre entier supérieur à 1
- Ar est sélectionné dans le groupe constitué de :
- X est un halogène, de préférence X est choisi parmi le fluor et le chlore, de préférence encore X est le fluor ;
- m is an integer greater than 1
- n is 0 or an integer greater than 1
- the m/n ratio is between 100/0 and 1/99, preferably between 100/0 and 10/90
- p is an integer greater than 1
- Ar is selected from the group consisting of:
- X is a halogen, preferably X is chosen from fluorine and chlorine, more preferably X is fluorine;
Dans un mode de réalisation particulier, le ratio m/n du polymère de formule (I) est de 100/0. Le polymère de l'invention se présente alors sous la forme d'un homopolymère comprenant le motif de répétition de formule (IV) suivante :
- p est un nombre entier supérieur à 1
- Ar est sélectionné dans le groupe constitué de :
- X est un halogène, de préférence X est choisi parmi le fluor et le chlore, de préférence encore X est le fluor.
- p is an integer greater than 1
- Ar is selected from the group consisting of:
- X is a halogen, preferably X is chosen from fluorine and chlorine, more preferably X is fluorine.
Selon ce dernier mode de réalisation où le ratio m/n est égal à 100/0, un polymère particulièrement préféré est celui de formule (V) suivante :
- p est un nombre entier supérieur à 1
- X est un halogène, de préférence X est choisi parmi le fluor et le chlore, de préférence encore X est le fluor.
- p is an integer greater than 1
- X is a halogen, preferably X is chosen from fluorine and chlorine, more preferably X is fluorine.
L'invention concerne également un procédé de préparation du polymère de type polyéther aromatique comprenant le ou les motifs de répétition de la formule (I).The invention also relates to a process for preparing the aromatic polyether type polymer comprising the repeating unit(s) of formula ( I ).
Le procédé de préparation du polymère comprenant le ou les motifs de répétition de la formule (I) comprend une étape de réaction entre le tetrahydrofurane diméthanol, optionnellement en présence d'un co-diol HO-D-OH, avec un composé aromatique dihalogéné X-Ar-X en présence d'une base dans un solvant organique. Les co-diols et les composés aromatiques dihalogénés pouvant être utilisés sont ceux décrits ci-dessus..The process for preparing the polymer comprising the repeating unit(s) of formula ( I ) comprises a reaction step between tetrahydrofuran dimethanol, optionally in the presence of a co-diol HO- D -OH, with a dihalogenated aromatic compound - Ar -X in the presence of a base in an organic solvent. The co-diols and dihalogenated aromatic compounds which can be used are those described above.
De manière avantageuse, le procédé de l'invention permet de contrôler le ratio molaire entre le tetrahydrofurane diméthanol et le composé aromatique dihalogéné de manière à obtenir des polymères présentant une grande hydrophilie et/ou de bonnes propriétés de perméabilité.Advantageously, the process of the invention makes it possible to control the molar ratio between the tetrahydrofuran dimethanol and the dihalogenated aromatic compound so as to obtain polymers having high hydrophilicity and/or good permeability properties.
Cette hydrophilie importante est une propriété particulièrement intéressante pour la fabrication de membranes de filtration : ladite membrane va s'humidifier rapidement, ce qui conduit à une filtration rapide avec des débits et des rendements élevés.This significant hydrophilicity is a particularly interesting property for the manufacture of filtration membranes: said membrane will humidify quickly, which leads to rapid filtration with high flow rates and yields.
Ainsi, le procédé objet de la présente Demande est un procédé de préparation d'un polymère comprenant le ou les motifs de répétition de la formule (I),
- le ratio m/n est compris entre 100/0 et 1/99
- p est un nombre entier supérieur à 1
- Ar est sélectionné dans le groupe constitué de :
- D est sélectionné dans le groupe constitué de :
- X est un halogène, de préférence X est choisi parmi le fluor et le chlore, de préférence encore X est le fluor,
- the m/n ratio is between 100/0 and 1/99
- p is an integer greater than 1
- Ar is selected from the group consisting of:
- D is selected from the group consisting of:
- X is a halogen, preferably X is chosen from fluorine and chlorine, more preferably X is fluorine,
De manière générale, la masse moléculaire moyenne du polymère de la formule (I) est comprise entre 1 000 et 150 000 g/mol,.Generally speaking, the average molecular mass of the polymer of formula (I) is between 1,000 and 150,000 g/mol.
Une classe particulière de polymères objets de la présente Demande sont les polymères de formule (I) précitée, dont la masse moléculaire moyenne est comprise entre 40 000 et 150 000 g/mol, de préférence entre 70 000 et 150 000 g/mol.A particular class of polymers which are the subject of this Application are the polymers of formula (I) mentioned above, the average molecular mass of which is between 40,000 and 150,000 g/mol, preferably between 70,000 and 150,000 g/mol.
Des variantes du procédé selon l'invention, sont les variantes qui conduisent aux polymères de formules (II), (III), (IV) et (V), en opérant les choix relatifs aux composés X-Ar-X et HO-D-OH, au ratio m/n et à l'entier p, qui ont été explicités précédemment, en ce qui concerne lesdits polymères de formules (II), (III), (IV) et (V). Ces choix s'appliquent donc mutatis mutandis aux différentes variantes du procédé selon l'invention.Variants of the process according to the invention are the variants which lead to the polymers of formulas ( II ), ( III ), ( IV ) and ( V ), by making the choices relating to the compounds X- Ar -X and HO- D -OH, at the ratio m/n and at the integer p, which have been explained previously, with regard to said polymers of formulas ( II ), ( III ), ( IV ) and ( V ). These choices therefore apply mutatis mutandis to the different variants of the process according to the invention.
La réaction entre le tetrahydrofurane diméthanol, et optionnellement un co-diol, avec le composé aromatique dihalogéné est mise en oeuvre en présence d'une base dans un solvant organique et permet de former le polymère de l'invention.The reaction between tetrahydrofuran dimethanol, and optionally a co-diol, with the dihalogenated aromatic compound is carried out in the presence of a base in an organic solvent and makes it possible to form the polymer of the invention.
La base est avantageusement choisie parmi les sels de métaux alcalins. De préférence, la base est choisie parmi le carbonate de potassium (K2CO3), le carbonate de sodium (Na2CO3), le carbonate de césium (CsCO3), le carbonate de lithium (LiCO3), le méthanolate de potassium, le méthanolate de sodium, l'éthanolate de potassium, le tert-butylate de potassium, le tert-pentylate de potassium, le bis(triméthyl)silanolate de potassium, le bis(triméthylsilyl)amide de potassium, l'hydroxyde de potassium, l'hydroxyde de sodium, et l'hydrure de sodium. De préférence encore, la base est choisie parmi le carbonate de potassium et le carbonate de sodium. Encore plus préférentiellement, la base est le carbonate de potassium et le carbonate de sodium.The base is advantageously chosen from alkali metal salts. Preferably, the base is chosen from potassium carbonate (K 2 CO 3 ), sodium carbonate (Na 2 CO 3 ), cesium carbonate (CsCO 3 ), lithium carbonate (LiCO 3 ), methanolate potassium, sodium methanolate, potassium ethanolate, potassium tert- butoxide, potassium tert -pentylate, potassium bis(trimethyl)silanolate, potassium bis(trimethylsilyl)amide, potassium hydroxide potassium, sodium hydroxide, and sodium hydride. More preferably, the base is chosen from potassium carbonate and sodium carbonate. Even more preferably, the base is potassium carbonate and sodium carbonate.
Avantageusement, la proportion de base est comprise entre 1 et 3 équivalents en mole par rapport à la quantité totale de tetrahydrofurane diméthanol et de co-diol. De préférence, la proportion de base est d'environ 2 équivalents en mole par rapport à la quantité totale de tetrahydrofurane diméthanol et de co-diol.Advantageously, the proportion of base is between 1 and 3 mole equivalents relative to the total quantity of tetrahydrofuran dimethanol and co-diol. Preferably, the proportion of base is approximately 2 mole equivalents relative to the total quantity of tetrahydrofuran dimethanol and co-diol.
Le solvant organique est avantageusement choisi parmi les solvants polaires aprotiques. Par « solvant polaire aprotique », on entend au sens de la présente invention un solvant possédant un moment dipolaire sans atome d'hydrogène acide, c'est-à-dire lié à un hétéroatome. De préférence, le solvant est choisi parmi les solvants polaires aprotiques comprenant un atome de soufre ou un atome d'azote. De préférence encore, le solvant est choisi parmi le diméthylsulfoxyde, le diéthylsulfoxyde, le sulfolane, la diméthylsulfone, la diéthylsulfone, la diphénylsulfone, la diisopropylsulfone, le tétrahydrothiophène-1-monoxyde, le diméthylacétamide, le diméthylformamide, la N-méthyl-2-pyrrolidone, et la N-cyclohexyl-2-pyrrolidone, seuls ou en mélange. Plus préférentiellement, le solvant est choisi parmi la N-méthyl-2-pyrrolidone et le diméthylsulfoxyde, seuls ou en mélange. Encore plus préférentiellement, le solvant est le diméthylsulfoxyde ou la N-méthyl-2-pyrrolidone.The organic solvent is advantageously chosen from polar aprotic solvents. By “aprotic polar solvent” is meant for the purposes of the present invention a solvent having a dipole moment without an acidic hydrogen atom, that is to say linked to a heteroatom. Preferably, the solvent is chosen from polar aprotic solvents comprising a sulfur atom or a nitrogen atom. More preferably, the solvent is chosen from dimethylsulfoxide, diethylsulfoxide, sulfolane, dimethylsulfone, diethylsulfone, diphenylsulfone, diisopropylsulfone, tetrahydrothiophene-1-monoxide, dimethylacetamide, dimethylformamide, N-methyl-2- pyrrolidone, and N-cyclohexyl-2-pyrrolidone, alone or in mixture. More preferably, the solvent is chosen from N-methyl-2-pyrrolidone and dimethyl sulfoxide, alone or as a mixture. Even more preferably, the solvent is dimethyl sulfoxide or N-methyl-2-pyrrolidone.
Dans un mode de réalisation, un co-solvant peut être ajouté au solvant organique. Le co-solvant est avantageusement choisi parmi le toluène, le benzène, le chlorobenzène, le tetrahydrofurane, seuls ou en mélange. De préférence, le co-solvant est le toluène.In one embodiment, a co-solvent may be added to the organic solvent. The co-solvent is advantageously chosen from toluene, benzene, chlorobenzene, tetrahydrofuran, alone or as a mixture. Preferably, the co-solvent is toluene.
Ainsi, le polymère est formé par réaction entre le tetrahydrofurane diméthanol, optionnellement un co-diol, et le composé aromatique dihalogéné en tant que monomères. Avantageusement, la proportion totale en monomères, c'est-à-dire la somme de la quantité de tetrahydrofurane diméthanol, de co-diol et de composé aromatique dihalogéné, est comprise entre 10% et 50%, de préférence entre 20% et 40% en masse par rapport à la somme de la masse du solvant et de la masse des monomères. De préférence encore, la proportion en monomères est d'environ 30% en masse par rapport à la somme de la masse du solvant et de la masse des monomères.Thus, the polymer is formed by reaction between tetrahydrofuran dimethanol, optionally a co-diol, and the dihalogenated aromatic compound as monomers. Advantageously, the total proportion of monomers, that is to say the sum of the quantity of tetrahydrofuran dimethanol, co-diol and dihalogenated aromatic compound, is between 10% and 50%, preferably between 20% and 40%. % by mass relative to the sum of the mass of the solvent and the mass of the monomers. More preferably, the proportion of monomers is approximately 30% by weight relative to the sum of the mass of the solvent and the mass of the monomers.
Afin de démarrer la réaction entre le tetrahydrofurane diméthanol, optionnellement un co-diol et le composé aromatique dihalogéné pour former le polymère, le milieu réactionnel comprenant le tetrahydrofurane diméthanol, optionnellement un co-diol, et le composé aromatique dihalogéné est chauffé. Avantageusement, la préparation du polymère est réalisée à une température comprise entre 160°C et 240°C, de préférence entre 190°C et 230°C, de préférence encore entre 200°C et 220°C, pendant une durée comprise entre 30 minutes et 12 heures, de préférence entre 30 minutes et 6 heures, de préférence encore entre 1 heure et 3 heures. Encore plus préférentiellement, le polymère est réalisée à une température d'environ 210°C, pendant une durée d'environ 2 heures.In order to start the reaction between tetrahydrofuran dimethanol, optionally a co-diol and the dihalogenated aromatic compound to form the polymer, the reaction medium comprising tetrahydrofuran dimethanol, optionally a co-diol, and the compound dihalogenated aromatic is heated. Advantageously, the preparation of the polymer is carried out at a temperature between 160°C and 240°C, preferably between 190°C and 230°C, more preferably between 200°C and 220°C, for a period of between 30 minutes and 12 hours, preferably between 30 minutes and 6 hours, more preferably between 1 hour and 3 hours. Even more preferably, the polymer is produced at a temperature of approximately 210° C., for a period of approximately 2 hours.
A l'issue de la réaction, le polymère obtenu peut être précipité par les techniques connues de l'homme du métier, comme par exemple la précipitation du milieu réactionnel dans un grand volume d'eau, environ 10 fois le volume du milieu réactionnel. Le polymère peut ensuite être séché selon les techniques connues de l'homme du métier comme par exemple dans une étuve à 80°C pendant 12 heures. Le polymère résultant peut enfin, de manière optionnelle, subir des étapes de post traitement, notamment en vue d'augmenter sa pureté ou d'améliorer certaines de ses propriétés.At the end of the reaction, the polymer obtained can be precipitated by techniques known to those skilled in the art, such as for example the precipitation of the reaction medium in a large volume of water, approximately 10 times the volume of the reaction medium. The polymer can then be dried according to techniques known to those skilled in the art, for example in an oven at 80°C for 12 hours. The resulting polymer can finally, optionally, undergo post-treatment steps, in particular with a view to increasing its purity or improving certain of its properties.
Un autre objet de la présente invention concerne l'utilisation du polymère selon l'invention pour la fabrication de membranes, de pièces manufacturées et de revêtement.Another object of the present invention relates to the use of the polymer according to the invention for the manufacture of membranes, manufactured parts and coatings.
Des membranes peuvent être fabriquées à partir du polymère selon l'invention selon les techniques connues de l'homme du métier.Membranes can be manufactured from the polymer according to the invention according to techniques known to those skilled in the art.
En particulier, les membranes obtenues avec le polymère à selon l'invention présentent des propriétés d'hydrophilie et de perméabilité aux gaz intéressantes. Les membranes peuvent se présenter sous forme de films poreux ou non poreux. Les membranes peuvent être fabriquées sous forme de mono filament ou de fibres creuses. Le polymère selon l'invention peut être utilisé dans les milieux aqueux, incluant les fluides corporels. Le polymère selon l'invention est biocompatible et peut donc être utilisé sous forme de membrane dans le milieu médical comme pour les hémodialyses ou dans le milieu de la consommation (alimentaire et boissons), dans le milieu du traitement des eaux usées. Les membranes poreuses sous forme de tubes ou de fibres creuses peuvent présenter différentes tailles de pores connues de l'homme du métier en fonction de leurs applications (microfiltration, ultrafiltration, nanofiltration, osmose inverse). Les performances des membranes aqueuses obtenues avec le polymère selon l'invention peuvent être améliorées par les techniques connues de l'homme du métier, en particulier l'utilisation de monomères sulfonés ou le post-traitement des membranes par sulfonation ou par traitement de surface pour éviter l'encrassement.In particular, the membranes obtained with the polymer according to the invention have interesting hydrophilic and gas permeability properties. The membranes can be in the form of porous or non-porous films. The membranes can be manufactured in the form of monofilament or hollow fibers. The polymer according to the invention can be used in aqueous media, including body fluids. The polymer according to the invention is biocompatible and can therefore be used in the form of a membrane in the medical environment such as for hemodialysis or in the consumer environment (food and drinks), in the wastewater treatment environment. Porous membranes in the form of tubes or hollow fibers can have different pore sizes known to those skilled in the art depending on their applications (microfiltration, ultrafiltration, nanofiltration, reverse osmosis). The performance of the aqueous membranes obtained with the polymer according to the invention can be improved by techniques known to those skilled in the art, in particular the use of monomers sulfonated or post-treatment of membranes by sulfonation or surface treatment to prevent clogging.
Les membranes en phase gazeuse peuvent servir à la production d'azote à partir de la séparation du mélange azote, oxygène de l'air, la production du méthane à partir de la séparation du méthane et du CO2.Gas phase membranes can be used for the production of nitrogen from the separation of the mixture of nitrogen and oxygen from the air, and the production of methane from the separation of methane and CO 2 .
Les membranes sous forme de films ou de plaques peuvent être utilisées pour l'optique ou pour l'emballage.Membranes in the form of films or plates can be used for optics or packaging.
Des pièces moulées peuvent être fabriquées à partir du polymère de l'invention selon les techniques connues de l'homme du métier. Le moulage à injection du polymère selon l'invention peut conduire à la production de pièces utilisées dans le secteur de la santé, avec des applications dentaires pour remplacer les métaux, le verre et d'autres ustensiles jetables ou réutilisables, mais aussi dans le secteur aéronautique, électronique et automobile.Molded parts can be manufactured from the polymer of the invention according to techniques known to those skilled in the art. Injection molding of the polymer according to the invention can lead to the production of parts used in the health sector, with dental applications to replace metals, glass and other disposable or reusable utensils, but also in the sector aeronautics, electronics and automobiles.
Un autre objet de cette invention est l'utilisation du polymère de l'invention en tant que résine de revêtement des métaux pour prévenir de la corrosion.Another object of this invention is the use of the polymer of the invention as a metal coating resin to prevent corrosion.
Le revêtement obtenu à partir du polymère selon l'invention peut être appliqué sur l'acier, l'aluminium, le cuivre, métaux utilisés dans le secteur de la consommation (alimentation et boisson), le secteur de la marine avec les coques des bateaux, les secteurs de l'aérospatial, de l'automobile, électrique avec les câbles et électronique avec les circuits. La résine obtenue à partir du polymère selon l'invention peut aussi être appliquée à d'autres substrats comme le verre ou la fibre de carbone pour former un composite après évaporation du solvant de la résine. Les composites formés à partir de la résine du polymère selon l'invention peuvent être utilisés dans le domaine aérospatial et automobile pour remplacer les pièces métalliques.The coating obtained from the polymer according to the invention can be applied to steel, aluminum, copper, metals used in the consumer sector (food and beverage), the marine sector with the hulls of boats , the aerospace, automotive, electrical with cables and electronics with circuits sectors. The resin obtained from the polymer according to the invention can also be applied to other substrates such as glass or carbon fiber to form a composite after evaporation of the resin solvent. The composites formed from the polymer resin according to the invention can be used in the aerospace and automotive fields to replace metal parts.
L'invention sera encore mieux comprise à la lecture des exemples qui suivent, lesquels se veulent purement illustratifs et ne limitent en rien la portée de la protection.The invention will be even better understood on reading the examples which follow, which are intended to be purely illustrative and in no way limit the scope of the protection.
Le tetrahydrofurane diméthanol et optionnellement un co-diol (5 mmol au total), le composé aromatique dihalogéné (5 mmol) et le carbonate de potassium (1,3961 g, 10 mmol) sont introduits dans un ballon tricol de 100 mL équipé d'une pale d'agitation, d'une entrée et d'une sortie d'azote pour éviter l'oxydation. L'ensemble est solubilisé dans le DMSO (5 mL) et est porté à 210°C avec une agitation de 50 rpm. Après 2 h à 9 h de chauffage à 210°C, le milieu est dilué avec 10 mL de DMSO. Lorsque le milieu est revenu à température ambiante, le polymère est précipité dans 100 mL d'eau distillée dans un bécher sous agitation magnétique. Après 1 h d'agitation le polymère est récupéré par filtration Büchner puis il est séché dans une étuve pendant 12 h à 80°C. Le polymère est analysé en SEC, RMN 1H et DSC.The tetrahydrofuran dimethanol and optionally a co-diol (5 mmol in total), the dihalogenated aromatic compound (5 mmol) and the potassium carbonate (1.3961 g, 10 mmol) are introduced into a 100 mL three-necked flask equipped with a stirring blade, a nitrogen inlet and outlet to avoid oxidation. The whole is dissolved in DMSO (5 mL) and is brought to 210°C with stirring at 50 rpm. After 2 h to 9 h of heating at 210°C, the medium is diluted with 10 mL of DMSO. When the medium has returned to room temperature, the polymer is precipitated in 100 mL of distilled water in a beaker with magnetic stirring. After 1 hour of stirring, the polymer is recovered by Büchner filtration and then dried in an oven for 12 hours at 80°C. The polymer is analyzed by SEC, 1 H NMR and DSC.
Les spectres 100MHz 13C ont été réalisés sur un Brüker Ascend™ 400 dans un tube en verre de 5mm dans le DMSO- d 6.The 100MHz 13 C spectra were carried out on a Brüker Ascend ™ 400 in a 5mm glass tube in DMSO- d 6 .
L'analyse de calorimétrie différentielle à balayage a été réalisée sur une DSC-Q5000 SA, TA Instruments, USA avec un débit de 50ml/min à l'azote à 10°C/min ou 20°C/min de 20°C à 300°C et dans un creuset en aluminium percé.The differential scanning calorimetry analysis was carried out on a DSC-Q5000 SA, TA Instruments, USA with a flow rate of 50ml/min with nitrogen at 10°C/min or 20°C/min from 20°C to 300°C and in a pierced aluminum crucible.
L'analyse des masses molaires a été réalisée par chromatographie d'exclusion stérique avec une colonne Agilent PLgel 5µm dans le DMF/LiBr à 50°C pendant 35min avec un débit de 0,5mL/min et en calibration PS.The analysis of molar masses was carried out by size exclusion chromatography with an Agilent PLgel 5µm column in DMF/LiBr at 50°C for 35min with a flow rate of 0.5mL/min and in PS calibration.
Le polymère 1 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (5 mmol) et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 1 is prepared according to the general procedure above from tetrahydrofuran dimethanol (5 mmol) and difluorodiphenyl sulfone (5 mmol) as a dihalogenated aromatic compound.
Le polymère 2 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (5 mmol) et de dichlorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 2 is prepared according to the general procedure above from tetrahydrofuran dimethanol (5 mmol) and dichlorodiphenyl sulfone (5 mmol) as a dihalogenated aromatic compound.
Le polymère 3 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (5 mmol) et de difluorobenzonitrile (5 mmol) en tant que composé aromatique dihalogéné.Polymer 3 is prepared according to the general procedure above from tetrahydrofuran dimethanol (5 mmol) and difluorobenzonitrile (5 mmol) as a dihalogenated aromatic compound.
Le polymère 4 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (5 mmol) et de difluorobenzophénone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 4 is prepared according to the general procedure above from tetrahydrofuran dimethanol (5 mmol) and difluorobenzophenone (5 mmol) as a dihalogenated aromatic compound.
Le polymère 5 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (1 mmol), de Bisphénol A (4 mmol) en tant que co-diol et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 5 is prepared according to the general procedure above from tetrahydrofuran dimethanol (1 mmol), Bisphenol A (4 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as dihalogenated aromatic compound. .
Le polymère 6 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (1,25 mmol), de Bisphénol A (3,75 mmol) en tant que co-diol et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 6 is prepared according to the general procedure above from tetrahydrofuran dimethanol (1.25 mmol), Bisphenol A (3.75 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as as a dihalogenated aromatic compound.
Le polymère 7 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (2 mmol), de Bisphénol A (3 mmol) en tant que co-diol et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 7 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2 mmol), Bisphenol A (3 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as dihalogenated aromatic compound. .
Le polymère 8 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (2,5 mmol), de Bisphénol A (2,5 mmol) en tant que co-diol et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 8 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2.5 mmol), Bisphenol A (2.5 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as as a dihalogenated aromatic compound.
Le polymère 9 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (3 mmol), de Bisphénol A (2 mmol) en tant que co-diol et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 9 is prepared according to the general procedure above from tetrahydrofuran dimethanol (3 mmol), Bisphenol A (2 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as dihalogenated aromatic compound. .
Le polymère 10 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (4 mmol), de Bisphénol A (1 mmol) en tant que co-diol et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 10 is prepared according to the general procedure above from tetrahydrofuran dimethanol (4 mmol), Bisphenol A (1 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as dihalogenated aromatic compound. .
Le polymère 11 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (2,5 mmol), de 4,4'-dihydroxydiphényle (2,5 mmol) en tant que co-diol et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 11 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2.5 mmol), 4,4'-dihydroxydiphenyl (2.5 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as a dihalogenated aromatic compound.
Le polymère 12 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (2,5 mmol), de Bisphénol S (2,5 mmol) en tant que co-diol et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 12 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2.5 mmol), Bisphenol S (2.5 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as as a dihalogenated aromatic compound.
Le polymère 13 est préparé selon le mode opératoire général ci-dessus à partir de tetrahydrofurane diméthanol (2,5 mmol), d'isosorbide (2,5 mmol) en tant que co-diol et de difluorodiphényle sulfone (5 mmol) en tant que composé aromatique dihalogéné.Polymer 13 is prepared according to the general procedure above from tetrahydrofuran dimethanol (2.5 mmol), isosorbide (2.5 mmol) as co-diol and difluorodiphenyl sulfone (5 mmol) as as a dihalogenated aromatic compound.
Les caractérisations des polymères selon l'invention 1 à 13 sont présentées dans le tableau 1.The characterizations of the polymers according to the invention 1 to 13 are presented in Table 1.
Le Polymère 14 un polyéthersulfone acheté chez ACROS ORGANICS 178910050 sous forme de granulés transparents. Ce produit est un polyéthersulfone à base de bisphénol A et de dérivé diphényle sulfone.
Ce tableau illustre les caractéristiques de procédé mis en eouvre, et certaines des caractéristiques physico-chimiques des polymères résultant. Il démontre bien la possibilité d'obtenir des polyéthers aromatiques avantageusement à partir d'un composé biosourcé.This table illustrates the characteristics of the process used, and some of the physicochemical characteristics of the resulting polymers. It clearly demonstrates the possibility of obtaining aromatic polyethers advantageously from a biosourced compound.
Une membrane est préparée à partir d'une solution du polymère à 20%m dans la NMP coulée sur une plaque en verre. Le solvant est ensuite évaporé à l'aide du cycle thermique suivant : 50°C pendant 12h, 80°C pendant 1 h, 120°C pendant 1 h, 150°C pendant 1 h et 200°C pendant 2 h. Après la cuisson une membrane est obtenue.A membrane is prepared from a solution of the polymer at 20% m in NMP cast on a glass plate. The solvent is then evaporated using the following thermal cycle: 50°C for 12 h, 80°C for 1 h, 120°C for 1 h, 150°C for 1 h and 200°C for 2 h. After cooking a membrane is obtained.
Des membranes ont été préparées selon le mode opératoire général ci-dessus à partir des polymères 1, 6 et 8 selon l'invention en comparaison avec une membrane préparée à partir d'un polymère commercial.Membranes were prepared according to the general procedure above from polymers 1, 6 and 8 according to the invention in comparison with a membrane prepared from a commercial polymer.
Les caractérisations appliquées aux membranes sont décrites ci-dessous :The characterizations applied to the membranes are described below:
L'angle de contact des membranes préparées à partir des polymères 1 et 8 selon l'invention a été mesuré avec l'eau et le diiodométhane selon le modèle de Owens, Wendt, Rabel et Kaelble.The contact angle of the membranes prepared from polymers 1 and 8 according to the invention was measured with water and diiodomethane according to the model of Owens, Wendt, Rabel and Kaelble.
La mesure de reprise en eau a été réalisée avec un appareil de Sorption Dynamique de Vapeur (DVS Q-5000 SA, TA Instruments) à la pression atmosphérique et à l'isotherme de 21°C avec un cycle sorption/désorption de 0 à 90% d'humidité.The water recovery measurement was carried out with a Dynamic Vapor Sorption device (DVS Q-5000 SA, TA Instruments) at atmospheric pressure and at the isotherm of 21°C with a sorption/desorption cycle from 0 to 90 % humidity.
Les résultats sont présentés dans le tableau 2.
Ces résultats montrent que l'hydrophilie des polymères selon l'invention augmente en fonction du taux d'incorporation du tétrahydrofurane diméthanol. En effet, la mesure d'angle de contact des membranes préparées à partir des polymères 1 et 8 permet d'attester de la mouillabilité des films contenant du THFDM par rapport à la référence de PES. L'augmentation de l'énergie de surface en fonction du taux d'incorporation du tétrahydrofurane diméthanol permet la création d'interactions plus fortes du film de polymère avec la goutte d'eau. Ceci conduit ainsi à une diminution de l'angle de contact de l'eau en fonction du taux d'incorporation du tétrahydrofurane diméthanol. Enfin, et de manière particulièrement avantageuse, les polymères selon l'invention présentent une capacité d'apsorption d'eau bien supérieure à la référence : cette hydrophilie beaucoup plus marquée est particulièrement avantageuse pour une membrane, dont la capacité à s'hydrater rapidement va conditionner son rendement et son efficacité.These results show that the hydrophilicity of the polymers according to the invention increases as a function of the rate of incorporation of tetrahydrofuran dimethanol. Indeed, measuring the contact angle of the membranes prepared from polymers 1 and 8 makes it possible to attest to the wettability of the films containing THFDM compared to the PES reference. Increasing the surface energy as a function of the tetrahydrofuran dimethanol incorporation rate allows the creation of stronger interactions of the polymer film with the water drop. This thus leads to a reduction in the contact angle of the water as a function of the rate of incorporation of tetrahydrofuran dimethanol. Finally, and in a particularly advantageous manner, the polymers according to the invention have a water adsorption capacity much greater than the reference: this much more marked hydrophilicity is particularly advantageous for a membrane, whose capacity to hydrate quickly goes condition its performance and effectiveness.
Les expériences sont réalisées à température ambiante. La manipulation consiste à insérer le film à étudier dans la cellule de perméation. Après une désorption sous vide secondaire de 16 h, l'expérience de perméation consiste à imposer une pression (3 bar) d'un gaz choisi dans le compartiment amont de la cellule et à mesurer la remontée de pression dans le compartiment aval de la cellule. La perméabilité est calculée à partir de la pente de la droite pression en fonction du temps dans le régime stationnaire, corrigée du vide statique si nécessaire. Les propriétés de perméation de gaz des membranes préparées à partir du polymère 6 selon l'invention ont été mesurées. Les résultats sont présentés dans le tableau 3.
Ces résultats montrent que la membrane préparée à partir du polymère 6 contenant seulement 25% en mole de THFDM présente une sélectivité pour le dioxyde de carbone par rapport à l'oxygène (6,29) supérieure à celle de la membrane de référence obtenue avec un PES commercial (2,3).These results show that the membrane prepared from polymer 6 containing only 25 mol% of THFDM has a selectivity for carbon dioxide relative to oxygen (6.29) greater than that of the reference membrane obtained with a Commercial PES (2.3).
Claims (13)
- An aromatic polyether type polymer of formula I comprising a repeating unit formed from a furanic bio-based diol and an aromatic compound X-Ar-X, and optionally a second repeating unit formed from a co-diol HO-D-OH and an aromatic compound X-Ar-X:
Ar is selected from the group consisting of:
- X is a halogen- m is an integer which is greater than 1- n is 0 or an integer which is greater than 1- the ratio m/n is comprised between 100/0 and 1/99- p is an integer which is greater than 1 - The polymer of formula (I) according to claim 1
- the ratio m/n is comprised between 100/0 and 1/99, preferably between 100/0 and 10/90- p is an integer which is greater than 1- Ar is selected from the group consisting of:
- D is selected from the group consisting of:
- X is a halogen, preferably X is selected from fluorine and chlorine, more preferably X is fluorine. - The polymer of formula (II) according to claim 1
- the ratio m/n is comprised between 100/0 and 1/99, preferably between 100/0 and 10/90- p is an integer which is greater than 1- D is selected from the group consisting of:
- X is a halogen, preferably X is selected from fluorine and chlorine, more preferably X is fluorine. - The polymer of formula (III) according to claim 1
- m is an integer which is greater than 1- n is 0 or an integer which is greater than 1- the ratio m/n is comprised between 100/0 and 1/99, preferably between 100/0 and 10/90- p is an integer which is greater than 1- Ar is selected from the group consisting of:
- X is a halogen, preferably X is selected from fluorine and chlorine, more preferably X is fluorine. - The polymer of formula (IV) according to claim 1
- p is an integer which is greater than 1- Ar is selected from the group consisting of:
- X is a halogen, preferably X is selected from fluorine and chlorine, more preferably X is fluorine. - The polymer of formula (V) according to claim 1
- p is an integer which is greater than 1- X is a halogen, preferably X is selected from fluorine and chlorine, more preferably X is fluorine. - A method for preparing a polymer comprising the repeating unit(s) of formula (I)
- m is an integer which is greater than 1- n is 0 or an integer which is greater than 1- the ratio m/n is comprised between 100/0 and 1/99- p is an integer which is greater than 1- Ar is selected from the group consisting of:
- D is selected from the group consisting of:
- X is a halogen, preferably X is selected from fluorine and chlorine, more preferably X is fluorine.and comprises a step of reaction between tetrahydrofuran dimethanol, optionally in the presence of a compound of formula HO-D-OH, with a dihalogenated aromatic compound of formula X-Ar-X, in the presence of a base in an organic solvent. - The method according to claim 7, characterised in that the tetrahydrofuran dimethanol/co-diol molar ratio is comprised between 100/0 and 1/99.
- The method according to claim 7 or 8, characterised in that the base is selected from the alkali metal salts.
- The method according to any one of claims 7 to 9, characterised in that the organic solvent is selected from the aprotic polar solvents.
- The method according to any one of claims 7 to 10, characterised in that the proportion of monomers is comprised between 10% and 50% by mass relative to the sum of the mass of the solvent and the mass of the monomers.
- The method according to any one of claims 7 to 11, characterised in that the reaction between tetrahydrofuran dimethanol, optionally in the presence of a co-diol, with a dihalogenated aromatic compound is carried out at a temperature comprised between 160°C and 240°C.
- A use of a polymer according to one of claims 1 to 6, for manufacturing membranes of manufactured parts and coatings.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1857546A FR3085039B1 (en) | 2018-08-20 | 2018-08-20 | AROMATIC POLYETHERS BASED ON A FURANIC DIOL BIOSOURCE |
| PCT/FR2019/000138 WO2020039128A1 (en) | 2018-08-20 | 2019-08-20 | Aromatic polyethers containing a biosourced furan diol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3841147A1 EP3841147A1 (en) | 2021-06-30 |
| EP3841147B1 true EP3841147B1 (en) | 2023-10-04 |
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| EP19780287.9A Active EP3841147B1 (en) | 2018-08-20 | 2019-08-20 | Aromatic polyethers containing a biosourced furan diol |
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| Country | Link |
|---|---|
| US (1) | US20210317265A1 (en) |
| EP (1) | EP3841147B1 (en) |
| JP (1) | JP2021535246A (en) |
| KR (1) | KR20220035016A (en) |
| FR (1) | FR3085039B1 (en) |
| WO (1) | WO2020039128A1 (en) |
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|---|---|---|---|---|
| KR101704475B1 (en) | 2014-08-25 | 2017-02-10 | 주식회사 삼양사 | Polysulfone copolymer having excellent chemical resistance and heat resistance and method for preparing the same |
-
2018
- 2018-08-20 FR FR1857546A patent/FR3085039B1/en active Active
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2019
- 2019-08-20 US US17/269,637 patent/US20210317265A1/en active Pending
- 2019-08-20 KR KR1020217007849A patent/KR20220035016A/en not_active Application Discontinuation
- 2019-08-20 EP EP19780287.9A patent/EP3841147B1/en active Active
- 2019-08-20 WO PCT/FR2019/000138 patent/WO2020039128A1/en unknown
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| Publication number | Publication date |
|---|---|
| FR3085039B1 (en) | 2020-10-23 |
| US20210317265A1 (en) | 2021-10-14 |
| EP3841147A1 (en) | 2021-06-30 |
| FR3085039A1 (en) | 2020-02-21 |
| JP2021535246A (en) | 2021-12-16 |
| KR20220035016A (en) | 2022-03-21 |
| WO2020039128A1 (en) | 2020-02-27 |
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